Recovery of alkenyl-aromatic monomers by falling strand devolatilization

ABSTRACT

Disclosed is a process for the continuous on-line recovery of alkenylaromatic monomer from a polymer-monomer melt and for the removal of alkenylaromatic oligomers and high boiling organic compounds from the thus-removed monomer. The process comprises subjecting a polymer-monomer melt to a two-stage falling strand devolatilization step, contacting the vapor stream from the first devolatilization stage with a liquid stream in a first contacting zone to remove oligomer and high boilers from the vapor stream and concurrently enrich the monomer content thereof, contacting the vapor stream from the second devolatilization stage with a cooled liquid in a second contacting zone to condense the vapor stream, and adding a portion of the condensed vapor stream to the liquid stream in the first contacting zone.

United States Patent 1 [111 3,886,049

Bir et al. 1 May 27, 1975 RECOVERY OF ALKENYL-AROMATIC MONOMERS BY FALLING STRAND DEVOLATILIZATION Inventors: Wallace G. Bir, Creve Coeur, Mo.;

Joseph Novack, Springfield, Mass.

Assignee: Monsanto Company, St. Louis, Mo.

Filed: Mar. 9, 1973 Appl. No.: 339,784

Primary ExaminerNorman Yudkoff Assistant Examiner-Frank Sever Attorney, Agent, or Firm-Joseph 8. Nelson; Edward P. Grattan; James C. Logomasini [57] ABSTRACT [52} [15- Cl 203/ 203/ 2; 159/2 3; the thus-removed monomer. The process comprises 260/669 A subjecting a polymer-monomer melt to a two-stage l Cl 301d /0 C076 falling strand devolatilization step, contacting the [58] Field 0 Search /1 3; vapor stream from the first devolatilization stage with 159/ 260/669 3-5, 95 R, 95 95 a liquid stream in a first contacting zone to remove 264/204 oligomer and high boilers from the vapor stream and concurrently enrich the monomer content thereof. [56] References Cited contacting the vapor stream from the second devola- UMTED STATES PATENTS tilization stage with a cooled liquid in a second con- 2 m 802 5 1933 Hickman 203 72 acting Zone condense vapor stream and adding 11/1957 Twaddle at a]. 260/935 R a portion of the condensed vapor stream to the liquid 3,201,365 8/1965 Charlesworth er al zoo/93.5 A stream in the first contacting Zone- 3,450,l83 6 1969 Hinton 260 93.5 R 3,719,720 31973 Bir et al 260 1669 A 12 Clams 4 Drawmg FRST common SEPARATOK $2 7 r ri 20 24 EEVOLATILIZER RECEIVERS n REACTORS\ 1 22 H l l 92 SECXJ N D CON TACTOR PATENTEDMYZT ms SHEET whx 1 RECOVERY OF ALKENYL-AROMATIC MONOMERS BY FALLING STRAND DEVOLATILIZATION BACKGROUND OF THE INVENTION In recent years there has been an increasing interest in the production by continuous pass polymerization techniques of alkenylaromatic polymers, especially homopolystyrene and a rubber modifed graft copolymer of styrene polymerized on a pre-formed elastomeric substrate, this latter material known commercially as impact polystyrene. In such mass polymerization techniques, the polymer is first produced by continuous mass polymerization, and thereafter a stream of the polymer dispersed in styrene monomer, and sometimes containing other added polymers, is devolatilized to remove unpolymerized monomer and low boiling volatile materials therefrom. It has also been found in some cases that devolatilization can best be carried out in more than one stage, i.e., with more than one devolatilizer used in series. From the devolatilization apparatus there is emitted a stream or streams containing alkenylaromatic monomer vapor. The quantity of monomer thus emitted in such streams is so significant that recovery procedures are economically a necessity,

Heretofore a variety of alkenylaromatic monomer recovery procedures have been employed. In general, it is possible to condense the monomer and recycle it to the polymerization zone or zones of a continuous process. Typically, however, over a period of time the concentration of lower molecular weight but volatile alkenylaromatic oligomers, especially dimers and even trimers, tends to build up in a continuous system, and it is necessary in order to maintain a high standard of product quality to control or limit the amount of such oligomers returned from the one or more devolatilization zones to the polymerization zone or zones. In addition, it is necessary with certain of the styrene polymers that particular additives be incorporated therein during polymerization to ensure product quality. These additives include internal lubricants such as relatively long-chain fatty acids and esters, certain waxes, relatively high boiling hydrocarbons such as mineral oil and also dyes or tints, stabilizers and inhibitors in relatively very small quantities. While many of these additives are non-volatile in nature, the high heat conditions prevailing in the devolatilization procedures results in vaporization of certain of the long-chain fatty acids, esters and waxes as well as the high boiling hydrocarbons such as mineral oil. It is essential, in order to meet quality control, that the level of such additives not be re duced during the devolatilization procedure below a desired and specified quantity.

Another aspect of the overall mass alkenylaromatic polymerization system concerns the removal of oligomer from a sytrene monomer stream which has been recovered as pointed out above and is destined for recycling to an on-line polymerization reactor.

Heretofore, removal of oligomer from a monomer stream and subsequent recovery of additives therefrom has been done by offline distillation. A typical procedure involves the collection of condensate from the devolatilization zone followed by distillation thereof in a fractional distillation column capable of separating the oligomers and additives from the monomers. In general, prior art oligomer and additive separation techniques involve off-line process operations, typically practiced on a continuous basis.

There has now been discovered a technique for online recovery of monomer, removal of oligomers and recovery of high boiling additives from a stream of alkenylaromatic monomer vapor. The technique is relatively simple to utilize, can be conveniently incorporated into continuous polymerization equipment. typically for handling vapor directly issuing from the devolatilization zone or zones, and permits one to avoid the necessity for expensive and time-consuming off-line separation procedures. It also affords broad flexibility in controlling the amounts of separated oligomers and high boiling additives which can be recycled to the reaction zones of the process as well as the amounts thereof purged to maintain selected levels in continuous operations.

SUMMARY OF THE INVENTION The present invention is directed to a process for recovering alkenylaromatic monomer from a stream containing said monomer together with alkenylaromatic polymer, oligomers, high boiling organic compounds and inert hydrocarbons, and for reducing the concentration of oligomers and high boiling additives in a thusrecovered super-heated vapor feed stream composed of alkenylaromatic monomer, sometimes an organic solvent, alkenylaromatic oligomers, high boiling organic additives and miscellaneous hydrocarbons normally present as low level impurities in commercial grade alkenylaromatic monomer. In the second stage of this process, the vapor feed stream typically comprises at least about 60 weight percent monomer, and more typically at least about percent thereof, up to about 3 weight percent alkenylaromatic oligomers, up to about 3 weight percent high-boiling organic additives, and the balance up to percent of any given stream being inert hydrocarbons boiling within plus or minus 10C. of said monomer at 760 mmHg. These streams are typified by those obtained from the vacuum devolatilization step of a continuous mass polymerization plant carried out in multiple stages of devolatilization.

In accordance with the present invention, devolatilization is carried out in a falling strand devolitizing apparatus which will be defined in more detail herein below. In an exemplary devolatilization stage composed of two devolitalizers in series, wherein the second of such devolatilization operates at a somewhat lower pressure than the first, there are derived two separate vapor streams, each at a controlled, substantially constant sub-atmospheric pressure. Typically the pressures of these streams range from about 1 to 200 mmHg. and the temperature typically ranges from about to 320C, the conditions of pressures and temperatures for any given said stream being such that the stream is super-heated. A more typical temperature range is from about 200 to 260C,

The super-heated vapor stream from the first devolitalizing or flash distillation zone is charged to a first contacting and separation zone, also called a stripping zone. In this first contacting or stripping zone there is affected and intimate and turbulent mixing of the vapor stream with a liquid phase composed generally of the same ingredients as the vapor stream, but comprising generally different relative proportions of such components. Normally, the partial pressure of alkenylaromatic oligomer and high boiling organic com pounds over the liquid is less than in the vapor stream. After the vapor stream has been separated from the liquid phase. the concentration of styrene oligomers and hgh boiling additives in the resulting vapor stream is less than in the starting or charged vapor stream. The conditions of mixing or contacting the vapor stream with the liquid phase are preferably such that a near approach to thermal and mass equilibrium is achieved between the vapor and liquid phases.

In this contacting the separation step most of the super heat contained in the initially charged vapor stream is surrendered and utilized to vaporize a fraction of the alkenylaromatic monomer. solvent, if presem. and miscellaneous low boiling hydrocarbons from the liquid phase. At the same time, a fraction of the oligomer content and the high boiling additive content of the vapor stream is condensed into the liquid phase. Generally the pressure within the mixing and contacting zone may range from l to 200 mmHg. absolute and the temperature may range from about (1to 120C, with the lower portion of this temperature range being preferred to minimize coincidental polymerization in the liquid phase. An efficient separation of vapor phase from liquid phase is then affected, and the resulting vapor is discharged as a vapor exit stream from the stripping or separation zone. The vapor discharge characteristically has a relatively low degree of super heat, preferably substantially no super heat. and a relatively low oligomer and high boiling additive content as compared to the charged vapor stream. It is, thus. essen tially pure alkenylaromatic monomer which is suitable for recycling to an on-line polymerization apparatus.

Concurrently with the above, the vapor stream from the second stage of devolatilization, usually at a some what lower pressure than the first, is directed to a second contacting zone associated with the second stage devolatilizer. in this second contacting zone the vapor stream is contacted with a cooled liquid phase composed of essentially pure alkenylaromatic monomer, but cooled to a temperature below 25C and preferably refrigerated to a temperature of from about -l() to i0C. Contact of the heated vapor stream with cooled or refrigerated liquid phase in the second contacting zone effectively condenses practically all of the vapor stream so that the product from this second Zone is virtually an entirely liquid phase. A very small quantity of low boiling impurities. i.e.. non-condensables. and a trace of monomer which is not fully condensed. are both vented from this second contacting zone. but preferably after again washing with cooled or refrigerated liquid phase to condense the greatest possible quantity of the vapor.

A portion of the product liquid phase stream from this second contacting zone is directed through a heat exchange apparatus, preferably refrigeration apparatus. to lower the temperature thereof to below 25C, and preferably below 10C after which it is returned to the second contacting zone to contact additional vapor.

The second portion of the condensed liquid stream. optionally containing additional make-up monomer. is directed to the first contacting and separation or strip ping zone as additional contacting liquid therein. in this first zone. as detailed above. part of the alkenylaromatic monomer is vaporized and the al kenylaromatic oligomers and high boiling additives present therein are condensed into this circulating liquid phase stream. Separated liquid stream from the first Gill contacting and separation or stripping zone is continu ously recycled to the contacting zone of such stripper. The vapor stream exiting the first contacting and separation zone is subsequently externally condensed for recycle to one or more polymerization zones to supply a portion of the fresh monomer therein or for storage and use by any convenient means. Within the sump portion of the separation and stripping zone there is maintained a sufficient inventory of liquid for effective mixing and contacting of the vapor stream charged therewith. This liquid inventory is achieved by the continuous addition to the first stripping or separation zone of liquid monomer-rich condensate stream from the second contacting zone as detailed above. The flow rate of the liquid feed stream recycled to the stripping zone is typically controlled by level control means in the separate liquid sump portion of the stripping zone itself. The composition of the liquid supplied to the mixing or contacting region of the stripping zone is gencrally such that the proportion of oligomer and high boiling in compounds in such iiquid is less than that proportion required for equilibrium with the charged vapor stream from the first devolatilization zone. Such a proportion is maintained in the liquid phase of the stripping apparatus by the continuous controlled withdrawal of a fraction of the separated liquid from the mixing zone as an exit or purged liquid stream. This exit or purged stream generally contains a higher proportion of both oligomers and high boiling additives than in the exiting vapor stream from this first contacting or stripping zone. The flow rate of such as exit liquid stream is typically controlled by temperature means in the separate liquid sump in the bottom of the stripping zone. The temperature is a sufficiently good and reliable inferential measure of liquid oligomer content of the liquid in the sump region, and therefore also within the stripping zone in the present invention because of the maintenance of substantially constant pressure conditions in the first contacting or stripping zone. A portion of the exit liquid stream from the first contacting and separation zone may also be recycled to an al kenylaromatic polymerization reactor. Furthermore, the need for an external source of monomer-rich liquid. i.e., condensate from the second contacting zone, can be minimized. or even eliminated. by providing a refrig eration unit in the liquid recycle loop of the first con tacting and separation zone.

BRlEF DESCRIPTION OF THE DRAWINGS The present invention is better understood by refer ence to the appended drawings wherein:

FIG. is a schematic and diagrammatic flow diagram illustrating how the monomer recovery and purification unit ofthe present invention is incorporated into a continuous alkenylaromatic polymerization process;

FIG. 2 illustrates an apparatus configuration for a falling strand devolatilization unit adapted for use in the separation of alkenylaromatic monomer in accordance with the present invention;

FIG. 3 illustrates an apparatus configuration for a contacting and separation unit adapted for use in the purification of separated alkenylaromatic monomer in the present invention; and

FIG. 4 illustrates an apparatus configuration for a second contacting unit adapted for use in the separation and recovery of alkenylaromatic monomer in the present invention.

DETAILED DESCRIPTION OF THE INVENTIGN The present invention relates to the on-line recovery of alkenylaromatic monomers by separation of same from compositions consisting primarily of alkenylaromatic high polymers in combination with such monomers, and to the purification of the thus recovered monomers to eliminate therefrom undersirable oligomers and high boiling organic compounds. In contradistinction to the customary off-line techniques heretofore employed to accomplish the foregoing results, it is possible in accordance with the present invention to satisfactorily recovery and purify alkenylaromatic monomer in a completely on-line system adapted for continuous operation. The significant advantages resulting from employment of the present inventive techniques include the elimination of undesirable hold-up times associated with off-line procedures, as well as the flexibility offered by virtue of the continuous nature of the technique thereby permitting accommodation of a wide variety of product formulations. Specifically, the amount and chemical makeup of recycle streams can be conveniently monitored and altered by purging selected amounts of either high boiler-rich or low boiler-rich fractions which result in accordance with the present invention. Likewise, the technique of the present invention permits accommodation of practically any of the wide variety of additives which are conventionally incorporated into alkenylaromatic polymers to achieve particular desired product formulations, and loss of such additives is practically prevented in accordance with the present invention.

The term alkenylaromatic monomer" as employed in the present application is intended to encompass both styrene itself as well as the conventionally utilized derivatives thereof including the alkyl substituted styrenes such as alpha-methyl styrene, and the halogenated styrenes such as para-bromo styrene, paradichloro styrene, and the like. similarly, by the term alkenylaromatic polymer, it is intended to include those materials resulting from polymerization of the aforementioned monomers, including homopolymers and copolymers of same in addition to graft copolymers produced by polymerization of one or more of said monomers in the presence of a preformed polymeric material, such as a diene polymer. The detailed description of the present invention, however, will be set forth with reference to the polymerization of styrene, the most conventionally employed alkenylaromatic monomer, with the intention that the same will be deemed illustrative of the entire class of alkenylaromatic compounds.

The present invention will also be described with reference to certain additives and impurities which may be present in the various styrene polymer and mixed monomer and polymer streams throughout the polymerization, recovery and purification systems. In the class of additives are included internal lubricants such as relatively long-chain fatty acids and esters, certain waxes, relatively high boiling hydrocarbons such as mineral oil and also dyes or tints, stabilizers and inhibitors in relatively small amounts. It is the members of this class of materials which generally makes up the high-boiler" portion of any stream. In addition, however, the terms high-boiler, higher boiling fraction" and fraction of low volatility are used interchangably throughout the present application to include higher boiling organic impurities which are present, albeit in small amounts, in any styrene feedstock. Similarly, there is present in most commercial styrene feedstocks certain lower boiling inert hydrocarbon impurities in trace amounts such as ethylbenzene, cumene and the like. Constituents of this type generally make up the class of materials known as low-boilers". Furthermore, while reference is made throughout to the presence of the foregoing constituents, it is to be understood that the principles of the present invention are still applicable where one or more of these additional components is absent.

Referring now to the drawings, in FIG. I there is illustrated the general configuration of the recovery and purification unit in accordance with the present invention as well as its incorporation into a continuous mass polymerization process for polystyrene. The recovery and purification unit is made up of the combination of a two-stage falling strand devolatilization unit 30 for separation of styrene monomer and other volatile components from the product styrene polymer stream, a first contacting and separation chamber 60 for purification of a first styrene monomer vapor stream from the devolatilizer 30 by removing styrene oligomer and any high boiling components from said vapor stream, and a second contacting unit which serves to recover all styrene monomer further vaporized in the second stage of the devolatilization unit 30. Each of these three basic individual units will be described in detail hereinafter.

In the general overall process illustrated in FIG. 1, styrene monomer is mass polymerized continuously in a reactor portion of the system, preferably by means of a combination of two reactors l0 and 11 connected in series as illustrated in the drawing, to a conversion of from about 60 to 90%, as desired. A melt comprising the product polymer dispersed and dissolved in the unpolymerized monomer is conveyed from the second reactor 11 to the two-stage falling strand devolatilizer 30 wherein substantially all of the monomer is removed except for a residual amount which is less than l% and typically less than about 0.2%.

From the first stage 31 of devolatilizer 30, a vapor stream 33 is withdrawn and fed to the contacting and separation device 60 wherein the vapor stream is contacted with a liquid of appropriate composition to remove substantially all of the styrene oligomer and high boiling component of the vapor'stream. After separation from such liquid, the vapor stream exits from device 60 and passes through a pipe 62 to a condensing unit 20. The liquified condensate passes from the condenser 20 into a receiver 21, from whence it is pumped and recycled back to reactor 10.

A second vapor stream 34 is withdrawn from the sec 0nd stage 32 of the devolatilizer 30 and is fed to the second contacting device 90 wherein it is directly and intimately contacted with a stream of refrigerated liquid, thereby effecting condensation of substantially the entire vapor stream, save for a trace amount of styrene monomer and other non-condensable materials which are subsequently vented via line 91. The liquid condensate from contactor 90 is withdrawn and recycled through a refrigerating unit 92, with a portion thereof subsequently being recycled back into the contacting unit 90 via line 93 to provide the aforementioned refrigerated condensing liquid and with a second portion thereof being conducted via line 95 to the first contacting and separation unit 60 where it is added to the supply of contacting liquid employed therein. This contacting liquid in unit 60, which becomes increasingly concentrated with styrene oligomer and high boilers, is continuously withdrawn at the bottom of the unit and is recycled for reintroduction into the upper portion thereof. In this recycle loop 63 there is provided an exit line 64 through which a portion of the contacting liquid may be selectively purged or recycled back to reactor 11, or both concurrently. A purge 22 for low boiling components is provided in recycle line 23 carrying condensed styrene vapors to reactor 10 from contacting and separation unit 60 and the second reactor 11 via condenser and receiver 21 and condenser 24 and receiver 26, respectively.

Turning now to FIG. 2, there is seen illustrated one embodiment ofa falling strand devolatilizer suitable for the practice of the present invention, such devolatilizer being designated in its entirety by the reference numeral 30. Falling strand devolatilizer 30 can be considered to be composed of a shell and tube heat exchanger assembly herein designated by the numeral 35, a first flash tank 36 and a second flash tank 37.

The heat exchanger assembly 35 is comprised of a shell and tube exchanger body section 38 in a bonnet or header section 39. Within the body section 38 are mounted a plurality of spaced. parallel tubes composed of steel or the like. Tubes 40 extend between and are mounted into at their respective opposite end regions a pair of plates 41, as by welding or the like, the plates, as are all other elements in this heat exchanger, being typically composed of steel or the like. Spacing between the plates and rigidity for the entire assembly of plates 41 and tubes 40 is augmented by tie rods 42. Tubes 40 are thus placed in sealing engagement with plates 41. Tubes 40 are circumferentially encased by a shell or wall 43, thereby to provide a generally sealed interior region between tubes 40 and the interior wall of shell 43 for circulation of heat transfer fluid.

The first and second flash tanks 31 and 32 of devolatilizer 30 are of double walled jacketed construction for the purpose of controlling the interior temperature of the tanks during operation of the devolatilizer. A vapor take-off port is provided by the pipe and flange assembly 45 which communicates with the interior space of the tank 31 and a second vapor take-off port is provided in the second flash tank by means of pipe 55. The second flash tank 32 communicates with the first flash tank 31 by means of the interconnecting pipe 46. The shell and tube assembly 35 is mounted atop and protrudes into the flash tank 31. Hot melt to be devolatilized in conveniently input into bonnet 39 via pipe and flange assembly 47 which interconnects with the pipe and flange assembly 48. Pipe and flange assembly 47 interconnects with a melt pump (not shown) which is adapted to input into the heat exchanger assembly 35 an appropriate composition to be devolatilized.

In order to control the movement of material from the bottom regions of the flash tank 31 into the second flash tank 32 through the pipe 46, the falling strand devolatilizer has conveniently mounted across and within pipe 46 a plug type valve assembly (details of the plug not being shown) which is adapted to regulate the rate of egress of fluid material from the bottom of flash tank 31 into tank 32. Such a valve assembly includes a long-stem 49 which extendsupwardly through the flash tank 31 and through an appropriate channel actually located in the heat exchanger assembly 35, actually through the pipe and flange assembly 47 to project into a pedestal 50, there being an appropriate sealing means about the valve stem 49 in the upper region of the pipe and flange assembly 47. An actuator assembly 51 on the top side of pedestal 50 has a shaft 51 which engages the upper end of the stem 49 by means of a collar 53. The actuator 5 l is responsive to a level senser assembly (not shown) adapted to measure fluid level in the bottom region of tank 31. A controller assembly (not shown) couples the level senser with the actuator assembly S1 to complete the remote control of a poweractuated valve assembly in the base of the tank 31.

In operation, the heated composition to be devolatilized enters the tank 31 from the bottom of exchanger assembly 35 and the monomer vapor is promptly flashed away from the polymer melt. The vapor is taken off through pipe and flange assembly 45 in the top of tank 31. The annular area 56 defined within vessel 31 by the inner walls thereof and the adjoining wall of heat exchanger assembly 35 acts as a manifold-like device to collect the vapor and direct it out pipe and flange assembly 45. By having the heat exchanger assembly 35 recessed in the upper region of the tank 31, the tendency of polymer to be thrown within the tank 31 radially sidewardly and hence into the mouth of the pipe and flange assembly 45 is avoided. The once devolatilized material is then permitted to pass from the first flash tank 31 into the second flash tank 32 immediately therebeneath by means of gravity flow. Because the second flash tank 32 is at a lower pressure than the first flash tank, any residual monomer contained in the polymer melt is flashed away in the second stage and withdrawn by means of pipe 55.

The polymer melt material introduced into the falling strand devolatilizer of the present invention typically contains from about 60 to weight per cent styrene polymer, l0 to 40 weight per cent styrene monomer and minor amounts of the aforementioned additives and impurities. [t is fed to the preheater at temperatures from about and 240C. and exits therefrom at a temperature within the range of about 200 to 280C. The pressure at which the first flash tank 31 is held ranges from about 30 to 760 mms. of HgA, preferably 30 to 200 mms. HgA., whereas the pressure of the second flash tank 32 typically is held within the range of from about I to 40 mms. of HgA. The temperature in both of the devolatilization stages is maintained at between about 200 and 250C. The amount of vaporized material withdrawn from the first tank is generally approximately 10 times the amount of vaporized material which is obtained from the second devolatilization stage. [n all cases, the monomer content of the final polymer product exiting the bottom of the second flash tank 32 is less than 1%, and in most cases is less than about 0.2% by weight.

For further details concerning the falling strand devolatilization apparatus described above, reference is made to U.S. patent application Ser. No. 322,261 filed Jan. 9, l973, the disclosure of which is hereby incorporated by reference.

Referring now to FIG. 3, there is illustrated in detail the contacting and separation apparatus 60 which is employed in accordance with the present invention to purify the styrene vapor stream which has been recovered in falling strand devolatilization apparatus 30. The apparatus assembly consists of a generally cylindrical tank 65 fabricated preferably from steel or the like.

The tank 65 contains a side input pipe 66 which is adapted to receive the styrene vapor stream withdrawn from the first devolatilization tank 31 of devolatilizer 30. Tank 65 also contains at its upper end an exit pipe 67 through which the purified styrene vapor stream ultimately exits from contacting and separation device 60, as well as second exit pipe 68 located at the bottom of the tank and serving for the withdrawal of the contacting liquid 69 circulated within the tank. A second input pipe 70 is located on the side of tank 65 near the top portion thereof and this pipe serves as an input for the contacting liquid 69. Inside of tank 65 are positioned a series of three vertically arranged sieve trays 71 arranged in the conventional staggered manner. Associated with the contacting and separation tank 60 is a contacting liquid recycle loop 63 which begins at the exit pipe 68 for the contacting liquid at the bottom end of tank 65 and continues through pump 72 back up to the inlet pipe 70 at the top of the tank where the contacting liquid is reintroduced. The recycle loop 63 also contains therein a refrigeration unit 73 in parallel with a bypass line 74, which by the selection of an appropriate three-way valve permits the selective passage of some, all or none of the contacting liquid through the refrigeration unit.

Those skilled in the art will appreciate, under certain conditions the need for an external source of styrene monomer rich liquid may be eliminated through the se lective employment of the refrigeration means in the liquid recycle loop, should such a procedure provide better economics in a particular instance. It is important only that the oligomer and high boiling fraction content in the liquid phase in the contacting device be carefully controlled, as will be discussed in more detail hereinafter.

Also located in the recycle loop 63 are an input line 95 which supplies styrene monomer rich liquid from an external source, i.e., the contactor 90, to replenish the contacting liquid 69 and a purge line 64 through which oligomerand high boiler-rich contacting liquid may be selectively withdrawn to maintain the appropriate level and composition of contacting liquid 69 within the contacting and separation unit 60. Appropriate control means 76 responsive to the level of contacting liquid in tank 65 is provided to regulate the input of styrene-rich liquid from contactor 90 and a similar temperature responsive control means 77 is provided to meter the withdrawal of contacting liquid through purge line 64.

In operation, styrene vapor containing oligomer, high boiling fractions and low boiling fractions is introduced at inlet pipe 66 and follows generally the path indicated by means of the arrows in FIG. 3, passing up through the sieve trays and the contacting liquid contained thereon and finally entering a separation region 78 above the uppermost tray, and thus only vapor is ultimately withdrawn from tank 65 through the vapor exit pipe 67.

As mentioned above, the contacting liquid in the unit 60 comprises a mixture of styrene monomer, styrene oligomers, high boiling compounds and inert hydrocarbons. The weight percentage of oligomers in such liquid is generally above the percentage of styrene oligomers in the vapor stream entering the unit; however, the partial presssure of oligomers over the liquid in the contacting zone is less than the partial pressure of oligomers in the vapor stream. The quantity of contacting liquid in the contacting zone (as well, in effect, as

the degree of contacting between such liquid and the vapor stream) is such that after the vapor stream has passed therethrough in the contacting zone, the resulting vapor is substantially free of super heat. The composition of the liquid in the contact region is generally such that the proportion of oligomers and high boiling compounds in the contacting liquid is greater than in the liquid feed stream charged to the contact zone but less than the proportion required for equilibrium with the charged vapor stream. In the contacting step, most of the super heat contained in the initially charged vapor feed stream is surrendered and utilized to vaporize a fraction of the styrene monomer and miscellaneous low boiling hydrocarbons from the liquid phase. Concurrently therewith, a fraction of the oligomer content and high boiling content of the vapor feed stream is condensed into the liquid phase. Generally, the pressure within the contacting zone may range from about 1 to 200 mms. HgA. and the temperature may range from about 0 to 120C, with the lower portion of these respective ranges being preferred to minimize coincidental styrene polymerization in the liquid phase. In some instances, it is preferable to continuously and simultaneously add a styrene polymerization inhibitor to the liquid in contacting and separation device 60 to substantially completely prevent styrene polymerization therein. The inhibitor is chosen so as to have a molecular weight great enough to keep the inhibitor out of the vapor phase and in the liquid phase, one particularly preferred suitable inhibitor being tertiarybutylcatecol. Addition rates for such an inhibitor are usually below about 0.05 weight per cent, based on the total weight of liquid.

Typically, the vapor feed stream comprises at least about 60 per cent styrene monomer, up to about 3 weight per cent styrene oligomers, up to about 3 weight per cent of high boiling compounds and the balance up to I00 weight per cent of any given stream being inert hydrocarbons boiling within i 10C. of styrene at 760 mms. Hg. The pressure of the feed stream generally ranges from about 1 to about 100 mms. Hg. and the temperature typically ranges from about 175 to 300C., and more particularly from about 250 and 280C. Preferably, the styrene content of the charged vapor stream is at least 80 weight per cent styrene monomer. Preferably also, thevapor stream is at a pressure of from about 40 to mms. HgA. and the contacting zone is also preferably at a pressure of from about 40 to 100 mms. l-lgA.

For example, the temperature of a particular vapor stream entering unit 60 at inlet pipe 66 is about C. and the stream comprises about 952.8 lbs/hr. styrene, about 7.55 lbs/hr. dimer, about 11.44 lbs/hr. trimer and about 28.3 lbs/hr. of hydrocarbons consisting primarily of a mixture of ethylbenzene and cumene. The temperature in the unit 60 is maintained at about 70C. and a pressure of 61 mms. l-lgA. The vapor stream exiting from the unit 60 through pipe 67 is at about 70C. and comprises about 1,750 lbs/hr. styrene, about 1 1b./hr. of dimers, about 1.8 lbs/hr. of trimer and about 51 lbs/hr. of low boiling hydrocarbons. The styrene monomer rich liquid added to the system through line 95 is at about 5C. and comprises about 817 lbs/hr. of styrene monomer. The purged stream exiting from line 64 is about 70C. and amounts to approximately 64 lbs/hr. withdrawn.

In another run, where, for example, the entering stream of styrene monomer vapor contains approximately 0.9% stearic acid which has been added as an internal lubricant. together with approximately 3.5% concentration of oligomer, it is noted that the exiting vapor stream contains only approximately 0.4% stearic acid and 0. l3 oligomer.

For further details regarding suitable contacting and separation apparatus, reference is made to U.Sw patent application Ser. No. l72,l88, now US. Pat. No. 3.7 l9,720, filed Aug. 16, 1971, the disclosure of which is hereby incorporated by reference.

Referring to FIG. 4, there is illustrated in detail the second contacting device 90 employed in accordance with the present invention to recover the residual styrene monomer contained in the vapor stream exiting from the second stage of the devolatilization apparatus 30. Contactor unit 90 consists of a generally cylindrically shaped tank 96 preferably fabricated from steel and is provided near its upper end with a vapor inlet pipe 97 to receive the aforesaid vapor stream and is provided at its bottom end with a condensate withdrawal pipe 98 through which the liquid condensate 99 within the device is removed. Near the lower end of the tank 96 on one side thereof is located an L-shaped vapor discharge conduit 100 culminating in a vent line 91. Positioned in vertically displaced relationship one above the other near the central vertical axis of the tank 96 are a plurality of spraying heads 101 which communicate by means of individual pipe 102 with a main manifold pipe 103 located outside of the tank wall. A series of identical spraying heads 101 are similarly positioned in the upstanding leg of L-shaped vapor discharge conduit 100. Each of these heads likewise communicate by means of a pipe 104 with an exterior manifold pipe 105. Each of the exteriorly located manifold pipes 103 and 105, and ultimately each of the spray heads is provided with a supply of refrigerated cooling liquid by means of recycle loop 106 which emanates from the condensate withdrawal pipe 98 and contains refrigeration unit 92 between this point and the termination of said recycle loop at the spraying heads 101. Recycle loop 106 also contains a feed line 107 for supplying additional styrene monomer to the system, if necessary, in order to provide makeup styrene monomer or to assure complete dissolving of any additives which may have been entrained in the vapor stream exiting from the second stage of the volatilization apparatus 30. Also provided in the recycle loop 106 is an exit line 95 through which a portion of the recycled. refrigerated cooling liquid may be withdrawn from the recycle loop and added to the contacting liquid supply 69 of contacting and separation apparatus 60 illustrated in FIG. 3.

In operation, the vapor stream exiting from the second flash tank 32 of devolatilization apparatus 30 enters contacting tank 96 by means of input pipe 97 and is intimately, directly contacted with the refrigerated cooling liquid being discharged from spraying heads 101, this cooling liquid having been cooled to a temperature below C., and preferably below l()C., by means of refrigeration unit 92 in recycle loop I06. As a result of the intimate contact with the cooling liquid, essentially all condensable components of the input vapor stream are condensed and become part of the cooling liquid supply 99. Any residual condensables are subjected to a second intimate contact with the cooling liquid as the vapor passes out of tank 96 and through the L-shaped vapor exit conduit by means of the additional spraying head 10] located therein. There is then vented to the atmosphere via line 91 the noncondensables containing only a trace of styrene monomer and other low boiling hydrocarbons. The ultimate liquid condensate product 99, which is almost pure in styrene monomer and contains only minor amounts of oligomer and high boiling compounds, optionally with additional pure styrene monomer added thereto. is withdrawn from the bottom of tank 96 and is subjected to cooling in refrigeration unit 92, whereupon a portion of the recycle stream is recycled back to the spraying heads 101 and a second portion of the refrigerated recycle stream is directed to the contacting and separation unit 60 to replenish the supply of contacting liquid 69 therein, if necessary.

Thus, there has been provided an on-line technique for the recovery and purification of alkenylaromatic monomers, whereby substantially 100% of the monomeric material is recovered for ultimate recycle to the polymerization reactors, and wherein this recovered monomer is continuously purified to remove a large portion of undesirable alkenylaromatic oligomer and high boiling organic hydrocarbons therefrom prior to the said recycle of the recovered monomer.

While the foregoing invention has been described and pointed out with reference to certain specific and preferred embodiments thereof, it is to be understood that no limitations are to be implied from the foregoing description. The protection to be afforded this subject invention is to be limited only by the scope of the claims appended hereto.

What is claimed is:

l. A continuous on-line process for recovery of alkenylaromatic monomer, selected from styrene, alkyl substituted styrenes and halogenated styrenes, from a stream containing alkenylaromatic monomer, alkenylaromatic high polymer, alkenylaromatic oligomers, high boiling organic compounds and inert hydrocarbons, and for reducing the concentration of alkenylaromatic oligomers and high boiling organic compounds in said recovered alkenylaromatic monomer, which process comprises the steps of continuously and simultaneously A. subjecting an alkenylaromatic polymer'monomer melt containing additionally alkenylaromatic oligomers, high boiling organic compounds, and inert hydrocarbons to falling strand devolatilization in at least two consecutive flash vaporization zones maintained at a temperature of from to 280C and a pressure of from I to 200 mm of Hg A, wherein the second vaporization zone is maintained at a lower pressure than the first vaporization zone;

B. contacting in a first contacting and separation zone a stream of vapor from the first flash vaporization zone with a liquid comprising a mixture of alkenylaromatic monomer, alkenylaromatic oligomers, high boiling organic compounds and inert hydrocarbons, whereby the vapor stream exiting said contacting and separation zone has a reduced concentration of oligomers and high boiling organic compounds compared to the entering stream of vapor, separating the resulting vapor from said contacting liquid and removing said resulting vapor stream;

C. directly contacting in a second contacting zone a stream of vapor from the second flash vaporization zone with a liquid having a temperature of less than 25C. to condense substantially all alkenylaromatic monomer, oligomers, high boiling organic compounds and inert hydrocarbons contained in said vapor stream from the second flash vaporization zone and removing a stream of condensed liquid from said second contacting zone;

D. passing at least a portion of said condensed liquid stream to said first contacting and separation zone as additional contacting liquid; and

E. collecting said contacting liquid from said first contacting and separation zone in a sump region associated with said first zone and circulating said contacting liquid back to said first contacting and separation zone while maintaining a desired level of said contacting liquid in said sump region.

2. The process as defined by claim I, further comprising the step of continuously and simultaneously recycling said vapor stream removed from said first contacting and separation zone to an on-line alkenylaromatic polymerization apparatus.

3. The process as defined by claim 1, further comprising the step of continuously and simultaneously adding to said stream of condensed liquid removed from said second contacting zone a fresh liquid stream consisting essentially of styrene monomer.

4. The process as defined by claim 1, further comprising the step of continuously and simultaneously passing a portion of said condensed liquid stream from said second contacting zone through a heat exchange zone and thereby reducing the temperature of said liquid stream to less than 25C and returning said portion of cooled liquid stream to said second contacting zone.

5. The process as defined by claim 1, further comprising the step of continuously and simultaneously removing from said circulating contacting liquid in the first contacting and separation zone a desired purge stream of liquid comprising an oligomer at high boiling organic compound concentrate at a rate such that the level of liquid in said sump region is maintained at a predetermined level.

6. The process as defined by claim I, wherein a styrene polymerization inhibitor is continuously and simultaneously charged to said contacting liquid in the first contacting and separation zone at a rate sufficient to substantially completely prevent alkenylaromatic polymerization in said liquid.

7. The process as defined by claim 6. wherein said inhibitor is tertiary-butylcatecol.

8. The process as defined by claim 1, wherein the temperature in said first contacting and separation zone is in a range of from about 0 to C. and the pressure in said zone ranges from about 1 to 200 mms. HgA.

9. The process as defined by claim 1, wherein said alkenylaromatic is styrene.

10. The process as defined by claim 1, wherein said alkenylaromatic polymer-monomer melt subjected to falling strand devolatilization comprises from about 60 to 90% alkenylaromatic polymer and from about 10 to 40% alkenylaromatic monomer.

11. The process as defined in claim 1, wherein said first flash vaporization zone is at a temperature of from about to 250C. and at a pressure of from about 30 to 200 mms. of HgA. and said second flash vaporization chamber is at a temperature of from about 200 to 250C. and at a pressure of from about I to 40 mms. of HgA.

12. The process as defined by claim 1, wherein said stream of vapor from the first flash vaporization zone comprises at least about 60 weight per cent alkenylaromatic monomer, up to about 3 weight per cent alkenylaromatic oligomers and the balance up to I00 weight per cent being high boiling organic compounds and inert hydrocarbons, said stream being super-heated at a temperature in the range of from about l75 to 320C. and being at a pressure from about 1 to 200 mms. of HgA. 

1. A CONTINUOUS ON-LINE PROCESS FOR RECOVERY OF ALKENYLAROMATIC MONOMER, SELECTED FROM STYRENE, ALKYL SUBSTITUTED STYRENES AND HALOGENATED STYRENES, FROM A STREAM CONTAINING ALKENYLAROMATIC MOMONER, ALKENYLAROMATIC HIGH POLYMER, ALKENYLAROMATIC OLIGOMERS, HIGH BOILING ORGANIC COMPOUNDS AND INERT HYDROCARBONS, AND FOR REDUCING THE CONCENTRATION OF ALKENYLAROMATIC OLIGOMERS AND HIGH BOILING ORGANIC COMPOUNDS IN SAID RECOVERED ALKENYLAROMATIC MOMONER, WHICH PROCESS COMPRISES THE STEPS OF CONTINOUSLY AND SIMULTANEOUSLY A. SUBJECTING AN ALKENYLAROMATIC POLYMER-MOMONER MELT CONTAINING ADDITIONALLY ALKENYLAROMATIC OLIGOMERS, HIGH BOILING ORGANIC COMPOUNDS, AND INERT HYDROCARBONS TO FALLING STRAND DEVOLATILIZATION IN AT LEAST TWO CONSECUTIVE FLASH VAPORIZATION ZONES MAINTAINED AT A TEMPERATURE OF FROM 170* TO 280*C AND A PRESSURE OF FROM 1 TO 200 MM OF HG A, WHEREIN THE SECOND VAPORIZATION ZONE IS MAINTAINED AT A LOWER PRESSURE THAN THE FIRST VAPORIZATION ZONE; B. CONTACTING IN A FIRST CONTACTING AND SEPARATION ZONE A STREAM OF VAPOR FROM THE FIRST FLASH VAPORIZATION ZONE WITH A LIQUID COMPRISING A MIXTURE OF ALKENYLAROMATIC MONOMER, ALKENYLAROMATIC OLIGOMERS, HIGH BOILING ORGANIC COMPOUNDS AND INERT HYDROCARBONS, WHEREBY THE VAPOR STREAM EXISTING SAID CONTACTING AND SEPARATION ZONE HAS A REDUCED CONCENTRATION OF OLIGOMERS AND HIGH BOILING ORGANIC COMPOUNDS COMPARED TO THE ENTERING STREAM OF VAPOR, SEPARATING THE RESULTING VAPOR FROM SAID CONTACTING LIQUID AND REMOVING SAID RESULTING VAPOR STREAM; C. DIRECTLY CONTACTING IN A SECOND CONTACTING ZONE A STREAM OF VAPOR FROM THE SECOND FLASH VAPORIZATION ZONE WITH A LIQUID HAVING A TEMPERATURE OF LESS THAN 25*C. TO CONDENSE SUBSTANTIALLY ALL ALKENYLAROMATIC MOMONER, OLIGOMERS, HIGH-BOILING ORGANIC COMPOUNDS AND INERT HYDROCARBONS CONTAINED IN SAID VAPOR STREAM FROM THE SECOND FLASH VAPORIZATION ZONE AND REMOVING A STREAM OF CONDENSED LIQUID FROM SAID SECOND CONTACTING ZONE; D. PASSING AT LEAST A PORTION OF SAID CONDENSED LIQUID STREAM TO SAID FIRST CONTACTING AND SEPARATION ZONE AS ADDITIONAL CONTACTING LIQUID; AND E. COLLECTING SAID CONTACTING LIQUID FROM SAID FIRST CONTACTING AND SEPARATION ZONE IN A SUMP REGION ASSOCIATED WITH SAID FIRST ZONE AND CIRCULATING SAID CONTACTING LIQUID BACK TO SAID FIRST CONTACTING AND SEPARATION ZONE WHILE MAINTAINING A DESIRED LEVEL OF SAID CONTACTING LIQUID IN SAID SUMP REGION.
 2. The process as defined by claim 1, further comprising the step of continuously and simultaneously recycling said vapor stream removed from said first contacting and separation zone to an on-line alkenylaromatic polymerization apparatus.
 3. The process as defined by claim 1, further comprising the step of continuously and simultaneously adding to said stream of condensed liquid removed from said second contacting zone a fresh liquid stream consisting essentially of styrene monomer.
 4. The process as defined by claim 1, further comprising the step of continuously and simultaneously passing a portion of said condensed liquid stream from said second contacting zone through a heat exchange zone and thereby reducing the temperature of said liquid stream to less than 25*C and returning said portion of cooled liquid stream to said second contacting zone.
 5. The process as defined by claim 1, further comprising the step of continuously and simultaneously removing from said circulating contacting liquid in the first contacting and separation zone a desired purge stream of liquid comprising an oligomer at high boiling organic compound concentrate at a rate such that the level of liquid in said sump region is maintained at a predetermined level.
 6. The process as defined by claim 1, wherein a styrene polymerization inhibitor is continuously and simultaneously charged to said contacting liquid in the first contacting and separation zone at a rate sufficient to substantially completely prevent alkenylaromatic polymerization in said liquid.
 7. The process as defined by claim 6, wherein said inhibitor is tertiary-butylcatecol.
 8. The process as defined by claim 1, wherein the temperature in said first contacting and separation zone is in a range of from about 0* to 120*C. and the pressure in said zone ranges from about 1 to 200 mms. HgA.
 9. The process as defined by claim 1, wherein said alkenylaromatic is styrene.
 10. The process as defined by claim 1, wherein said alkenylaromatic polymer-monomer melt subjected to falling strand devolatilization comprises from about 60 to 90% alkenylaromatic polymer and from about 10 to 40% alkenylaromatic monomer.
 11. The process as defined in claim 1, wherein said first flash vaporization zone is at a temperature of from about 170* to 250*C. and at a pressure of from about 30 to 200 mms. of HgA. and said second flash vaporization chamber is at a temperature of from about 200* to 250*C. and at a pressure of from about 1 to 40 mms. of HgA.
 12. The process as defined by claim 1, wherein said stream of vapor from the first flash vaporization zone comprises at least about 60 weight per cent alkenylaromatic monomer, up to about 3 weight per cent alkenylaromatic oligomers and the balance up to 100 weight per cent being high boiling organic compounds and inert hydrocarbons, said stream being super-heated at a temperature in the range of from about 175* to 320*C. and being at a pressure from about 1 to 200 mms. of HgA. 